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No Access Submitted: 20 August 1990 Accepted: 01 October 1990 Published Online: 04 June 1998

  • Rotational features in the fluorescence excitation spectrum of O(1D2) from vacuum ultraviolet laser photodissociation of O2

J. Chem. Phys. 94, 1060 (1991); https://doi.org/10.1063/1.460062
S. T. Gibson, B. R. Lewis, K. G. H. Baldwin, and J. H. Carver
more...View Affiliations
  • Research School of Physical Sciences, The Australian National University, Canberra, ACT 2600, Australia
View Contributors
  • S. T. Gibson
  • B. R. Lewis
  • K. G. H. Baldwin
  • J. H. Carver
ABSTRACT
Seventh‐order anti‐Stokes Raman‐shifted ultraviolet laser radiation is used to dissociate O2 in the 175–177 nm region of the Schumann–Runge band system, B 3Σ−u–X 3Σ−g. A cross section for the production of O(1D2) is deduced from the 762 nm fluorescence of O2(b 1Σ+g), a collisional de‐excitation product of O(1D2) and O2(X 3Σ−g). Step structure observed in the spectrum is attributed to rotational thresholds for absorption from X 3Σ−g to energies above the B 3Σ−u dissociation limit. The threshold energies define a limiting rotationless dissociation energy of 57 136.4±0.9 cm−1. Shape resonances, quasibound by the rotational barrier of B 3Σ−u, are observed for the first time in O2. A theoretical calculation of the cross section is in agreement with the measured cross section when the near‐dissociation outer limb of the B 3Σ−u potential has an R−5 long range form. The shape of the adopted potential is consistent with an avoided crossing with another 3Σ−u state near R=4.6 Å.

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  1. © 1991 American Institute of Physics.

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